EP3225305A1 - Process for obtaining heterogeneous acid catalysts based on mixed metal salts and use thereof - Google Patents
Process for obtaining heterogeneous acid catalysts based on mixed metal salts and use thereof Download PDFInfo
- Publication number
- EP3225305A1 EP3225305A1 EP17164236.6A EP17164236A EP3225305A1 EP 3225305 A1 EP3225305 A1 EP 3225305A1 EP 17164236 A EP17164236 A EP 17164236A EP 3225305 A1 EP3225305 A1 EP 3225305A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lithium
- aluminum
- acid catalysts
- heterogeneous acid
- obtaining
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 239000002184 metal Substances 0.000 title claims abstract description 51
- 239000003377 acid catalyst Substances 0.000 title claims abstract description 49
- 150000003839 salts Chemical class 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 47
- 229910001868 water Inorganic materials 0.000 claims abstract description 44
- 239000011777 magnesium Substances 0.000 claims abstract description 35
- 239000010936 titanium Substances 0.000 claims abstract description 35
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 30
- -1 aluminum lithium hydride Chemical compound 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims abstract description 16
- 239000011701 zinc Substances 0.000 claims abstract description 14
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- VMWZRHGIAVCFNS-UHFFFAOYSA-J aluminum;lithium;tetrahydroxide Chemical class [Li+].[OH-].[OH-].[OH-].[OH-].[Al+3] VMWZRHGIAVCFNS-UHFFFAOYSA-J 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 11
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 9
- 239000000017 hydrogel Substances 0.000 claims abstract description 8
- 150000001457 metallic cations Chemical class 0.000 claims abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 37
- 229910052782 aluminium Inorganic materials 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 14
- 229920002472 Starch Polymers 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 235000019698 starch Nutrition 0.000 claims description 13
- 239000008107 starch Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 12
- 150000004676 glycans Chemical class 0.000 claims description 12
- 229920001282 polysaccharide Polymers 0.000 claims description 12
- 239000005017 polysaccharide Substances 0.000 claims description 12
- 239000005995 Aluminium silicate Substances 0.000 claims description 11
- 235000012211 aluminium silicate Nutrition 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 11
- 150000002739 metals Chemical class 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 229910016287 MxOy Inorganic materials 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 229910052712 strontium Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 8
- 235000021317 phosphate Nutrition 0.000 claims description 8
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 6
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 claims description 6
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 6
- 235000011285 magnesium acetate Nutrition 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 239000011654 magnesium acetate Substances 0.000 claims description 5
- 229940069446 magnesium acetate Drugs 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- 238000005504 petroleum refining Methods 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229920000945 Amylopectin Polymers 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- DYKZEUFKJOSFSH-UHFFFAOYSA-K P([O-])([O-])([O-])=O.[Al+3].[Li+] Chemical compound P([O-])([O-])([O-])=O.[Al+3].[Li+] DYKZEUFKJOSFSH-UHFFFAOYSA-K 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- FYWVTSQYJIPZLW-UHFFFAOYSA-K diacetyloxygallanyl acetate Chemical compound [Ga+3].CC([O-])=O.CC([O-])=O.CC([O-])=O FYWVTSQYJIPZLW-UHFFFAOYSA-K 0.000 claims description 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000000265 homogenisation Methods 0.000 claims description 2
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003225 biodiesel Substances 0.000 abstract description 17
- 238000005809 transesterification reaction Methods 0.000 abstract description 17
- 235000015112 vegetable and seed oil Nutrition 0.000 abstract description 7
- 239000008158 vegetable oil Substances 0.000 abstract description 7
- 235000019737 Animal fat Nutrition 0.000 abstract description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical class [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 21
- 238000007792 addition Methods 0.000 description 17
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 15
- 239000012280 lithium aluminium hydride Substances 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 11
- 235000011007 phosphoric acid Nutrition 0.000 description 10
- 239000000499 gel Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 230000003993 interaction Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910001679 gibbsite Inorganic materials 0.000 description 6
- 239000002638 heterogeneous catalyst Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 6
- 229910018575 Al—Ti Inorganic materials 0.000 description 5
- 239000002841 Lewis acid Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 235000021588 free fatty acids Nutrition 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229910010084 LiAlH4 Inorganic materials 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 239000002815 homogeneous catalyst Substances 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- 229940043774 zirconium oxide Drugs 0.000 description 4
- 229910018134 Al-Mg Inorganic materials 0.000 description 3
- 229910018467 Al—Mg Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical class [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- VOLGAXAGEUPBDM-UHFFFAOYSA-N $l^{1}-oxidanylethane Chemical compound CC[O] VOLGAXAGEUPBDM-UHFFFAOYSA-N 0.000 description 2
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- BPNMMLCOFUEDKN-UHFFFAOYSA-J [Li+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical class [Li+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BPNMMLCOFUEDKN-UHFFFAOYSA-J 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000005112 continuous flow technique Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 229910000103 lithium hydride Inorganic materials 0.000 description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical class [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 2
- 239000004137 magnesium phosphate Substances 0.000 description 2
- 235000010994 magnesium phosphates Nutrition 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 235000015927 pasta Nutrition 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- BCTWNMTZAXVEJL-UHFFFAOYSA-N phosphane;tungsten;tetracontahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.P.[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W] BCTWNMTZAXVEJL-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910018523 Al—S Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 1
- 241000208818 Helianthus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- 241000221089 Jatropha Species 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910010092 LiAlO2 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 description 1
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 description 1
- 229910007440 ZnAl2 O4 Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 description 1
- 229940093471 ethyl oleate Drugs 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000011985 first-generation catalyst Substances 0.000 description 1
- 229910001676 gahnite Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000011986 second-generation catalyst Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 229940117972 triolein Drugs 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1808—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1811—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with gallium, indium or thallium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/043—Lithium aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
- C01F7/74—Sulfates
- C01F7/76—Double salts, i.e. compounds containing, besides aluminium and sulfate ions, only other cations, e.g. alums
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Definitions
- the present invention relates to:
- Acid catalysts may be defined as oxygen carbonyl activators of the ester to increase its reactivity to the attack of the alcohol, typically methanol. These acid catalysts can be classified in those with Brönsted acid sites because they have carbonyl oxygen interactions with catalytic proton (H + ) sites and those with Lewis acid sites because of interactions of carbonyl oxygen with cationic (M + ) sites in the catalyst.
- Figure 1 describes the above explained, emphasizing experimental evidence showing the type of acidity on the surface of the catalyst by pyridine adsorption measured on an infrared spectrum which describes the interaction of a Lewis base on an acid surface.
- the interaction of the acidic sites on the surface with the pyridine molecule generates different bands.
- the characteristics for Brönsted acid sites appear at 1,545 cm -1 and the characteristics for Lewis acid sites appear at 1,445 cm -1 and the intermediate band at 1,490 cm -1 for the two interactions:
- HPAs heteropolyacids
- HPAs heteropolyacids
- 12-tungstophosphoric acid (H 3 PW 12 O 40 ) is chosen because of its high activity since it shows a Keggin structure which is composed of a coordinated tetrahedral heteroatom of oxygen (PO 4 ) surrounded by 12 additions of atoms sharing coordinated octahedral oxygen atoms (WO 6 ) according to Oliveira CF et al. in Esterification of oleic acid with ethanol by 12-tungstophosphoric acid supported on zirconia. Appl Catal A-Gen 372: 153-161 (2010 ).
- zirconium-oxide catalyst for producing biodiesel, as well as preparation method and application of zirconium-oxide catalyst. 2014 "a zirconium oxide catalyst is claimed to produce biodiesel in a tubular reactor at a reaction temperature of 250-300° C, reaction pressure of 7 to 14 MPa and volume ratio of alcohol-oil of 0.5: 1 to 7 :1.
- the catalyst is characterized by containing zirconium oxide of 80-95 weight %, aluminum oxide of 2-18 weight %, 1 to 17% titanium dioxide, 5 to 25% sodium bicarbonate and 10 to 50 % of sodium chloride and in the patent document CN 103,706,384 "Preparation method of bio-diesel catalyst” (2014), there is provided a method of preparing a catalyst for the production of biodiesel in a continuous flow process in which the composition is PO 4 3- / ZrO 2 doped with rare earth metals such as La, Ce, Pr, Nd, etc.
- Esterfip-H TM refers to a continuous process of transesterification where the reaction is promoted by a heterogeneous catalyst, which is a zinc aluminate (ZnAl 2 O 4 ) spinel, which promotes the transesterification reaction, without loss of catalyst.
- a heterogeneous catalyst which is a zinc aluminate (ZnAl 2 O 4 ) spinel, which promotes the transesterification reaction, without loss of catalyst.
- the reaction is carried out at an operating temperature of 180-220° C and pressure of 40-60 bar.
- the yields obtained are greater than 98%, with an excess of methanol.
- the raw material must have a free fatty acid content of less than 0.25% and a water content of less than 1,000 ppm. ( Juan A. Melero et al., Critical Review, Heterogeneous acid catalysts for biodiesel production: current status and future challenges, Green Chem., 2009, 11, 1285-1308 .)
- metal phosphates as metal catalysts for transesterification of biodiesel
- Xie et al. in Bioresource Technology (2012), 119, 60-65 , describe acid catalysts for transesterification of triglyceride esters based on 30 wt% WO 3 supported in AlPO 4 which were tested in batch reaction systems at 180° C for 5 h and a methanol / oil ratio of 30: 1 at a dose of 5% by weight catalyst.
- transesterification catalysis systems consist of calcium phosphates from animal bone pyrolysis, which generates hydroxyapatite at 800° C as described by Obadiah et al., in Bioresource Technology (2012), 116, 512-516 .
- Sodium phosphate has also been used as a transesterification catalyst for triglyceride esters in biodiesel production according to De Filippis et al., in Energy & Fuels (2005), 19 (6), 2225-2228
- the catalyst uses in its composition mixed metal salts, such as lithium and aluminum phosphates and sulfates, in addition to their combinations with metal cations such as magnesium, titanium, zinc, zirconium and gallium.
- the precursor of the mixed metal salts such as lithium and aluminum phosphates and sulfates, in addition to their combinations with metal cations such as magnesium, titanium, zinc, zirconium and gallium, come from a material product of the addition of water and oxygenated solvent, such as an ether, preferably tetrahydrofuran, diethyl ether or dimethoxyethane, on aluminum lithium hydride at temperatures of -20 to 60° C with stirring from 0-10,000 rpm , generating a dispersion of hydroxides of lithium and aluminum in water and oxygenated solvent, with a pH of 10 to 16, according to the reaction (1): LiAlH 4 + 4 H 2 O ⁇ LiOH + Al(OH) 3 + 4 H 2 (1)
- the catalyst is obtained from the addition of phosphoric acid or sulfuric acid to the mixture of lithium and aluminum hydroxides, product of the hydrolysis of lithium aluminum hydride (reaction 1), to obtain compositions of lithium: aluminum, phosphorous or sulfur and the incorporation of metals such as titanium and magnesium as promoters of Lewis acid sites from their acetic acid salts
- An additional object of these catalysts is their use in batch and continuous flow systems as promoters of reactions that require moderate Lewis acidity in various industries, such as petroleum refining, petrochemical and general chemistry.
- the present invention relates to:
- FIG. 2 shows in general terms the flow diagram by which some of the heterogeneous acid catalysts preferred by the present invention are obtained:
- the preparation of these catalysts consists of having a source of lithium and aluminum, such as the mixture of lithium and aluminum hydroxides or lithium aluminate, which are generated by the reaction of lithium aluminum hydride with water, forming a large quantity of hydrogen and the products described in reaction (1): LiAlH 4 + 4 H 2 O ⁇ LiOH + Al(OH) 3 + 4 H 2 (1)
- the lithium aluminate is formed by dissolving aluminum in lithium hydroxide, as a white precipitate, which by calcination generates 2Al 2 O 3 -Li 2 O ( Horan HA, Damiano JB "The Formation and Composition of Lithium Aluminate" J. Am. Chem. Soc., 57: 2434-2436, 1935 ).
- the flow chart shows the procedure for the preparation of the catalysts labeled HLPA and HLSA.
- the lithium and aluminum phosphates and/or sulfates to incorporate another Lewis acidity promoting cation such as titanium or magnesium, by means of a solution of titanium acetate or magnesium by a mixing step with agitation for 2-8 hours, preferably 2-3 hours.
- titanium and magnesium acetates are preferably prepared from the corresponding titanium and magnesium alkoxides, for example titanium isopropoxide or magnesium ethoxide; these alkoxides react with glacial acetic acid in stoichiometric proportions according to reactions (6) and (7): [(CH 3 ) 2 CHO] 4 Ti + 4 CH 3 COOH ⁇ (CH 3 COO) 4 Ti + 4 (CH 3 ) 2 CHOH (6) [CH 3 CH 2 O] 2 Mg + 2 CH 3 COOH ⁇ (CH 3 COO) 2 Mg + 2 CH 3 CH 2 OH (7)
- a graph in Figure 3 shows the Lewis acidity sites of the mixed metal salts heterogeneous acid catalysts of the present invention, HLPA, HLPAT and HLPAM series, respectively, as determined by Fourier Transform Infrared Spectrometry (FTIR).
- FTIR Fourier Transform Infrared Spectrometry
- the process of obtaining the heterogeneous acid catalysts of the present invention comprises the following steps:
- the heterogeneous acid catalysts preferred by the present invention are preferably composed of mixed metal salts such as lithium and aluminum phosphates and sulfates with the following percentages of metals by weight of the catalyst: lithium from 0 to 5 weight %, preferably from 0.1 to 3 weight %, and aluminum from 0 to 15 weight %, preferably from 0.3 to 10 weight %; in addition to their combinations with metal cations in concentrations of 0 to 40 weight % of the catalyst, preferably 0.2 to 30 weight %, such as magnesium, titanium, zinc, zirconium, gallium and silicon, which provide suitable Lewis acidity; organic or inorganic porosity promoters in concentrations of from 0.05 to 25 weight % of the wet base catalyst, preferably from 0 to 12 weight %, such as polysaccharides; and binders in concentrations of 1 to 20 weight % of the catalyst, preferably 3 to 15 weight %, such as clays, kaolin and metal oxides of the M x O y type, where M
- the physico-chemical properties of the heterogeneous acid catalysts of the present invention allow their use in batch reaction and continuous flow systems as promoters of reactions which require moderate Lewis acidity in various industries, such as petroleum refining, petrochemical and chemical.
- a magnetic stirrer was placed in a 500 mL three-necked round flask with 24/40 outlet. The flask was previously washed, rinsed with acetone and deionized water and dried into oven at 115° C for 24 h.
- a refrigerant was connected to the mouth central portion of the flask, having at the upper end a stopper (septa), in which a needle and a balloon filled with nitrogen gas (N 2 ) was inserted in order to generate an inert atmosphere in the system.
- a stopper sina
- N 2 nitrogen gas
- an addition funnel was placed using a glass stopper; in the other mouth of the flask a purge or vent plug was placed.
- the flask was placed in an ice bath with methanol and NaCl to avoid heating because of the exothermic reaction. Similarly, the arrangement of an inert atmosphere in the system was ensured by passing the nitrogen gas stream (N 2 ) contained in the balloon. 70 mL of freshly distilled anhydrous ether tetrahydrofuran (THF) was added to the flask thru the addition funnel; then agitation commenced. 14.3 g of lithium aluminum hydride (LAH) was placed in a 125 ml wide-mouth amber bottle with screw cap and inert atmosphere (nitrogen stream), previously dried at 120° C for 2 hours. Then, small portions (7 to 10 time) of anhydrous THF were added in the bottle aided by a plastic funnel.
- N 2 nitrogen gas stream
- LAH lithium aluminum hydride
- a white suspension was obtained in the first drop of the addition.
- the bath was maintained with sufficient ice and the continuous flow of N 2 through the system, allowing the gas mixture (H 2 -N 2 ) exiting the purge to be drawn towards the hood. Stirring was maintained at speeds lower than 1 RPM.
- the mixture obtained was a white dispersion of lithium and aluminum hydroxides in water and tetrahydrofuran, with a pH of 14, which was stored in a wide-mouth bottle, tightly closed and sealed for later use.
- Ortho-phosphoric acid was slowly added dropwise in a 100-mL beaker containing 20 g of the lithium aluminum hydroxide dispersion in water and tetrahydrofuran obtained in Example 1, the amount of the ortho-phosphoric acid was the necessary for having a concentration of 0.55% of P, on wet basis.
- the suspension was homogenized, first with a spatula and then with a magnetic stirrer to have a crystalline solution, then 4 g of the starch gel was prepared and added.
- the preparation of the starch gel was as follows: to 1 g of starch contained in a glass beaker, 30 mL of deionized water was added; the mixture was heated at 70° C for 30 min and taken to room temperature.
- the extruded catalyst prepared with metal/P weight ratio, on wet basis, of 1.2 Li/P and 4.7 AL/P was named as HLPA-16 heaving the following properties: surface area of 137 m 2 /g, pore volume of 0.25 cm 3 /g and average pore diameter of 73.4 ⁇ .
- the suspension was homogenized with stirring and the previously prepared crystalline solution of titanium acetate was added. While maintaining continuous stirring, more orthophosphoric acid was added into dropwise to obtain a phosphorus concentration of 4.2 wt % on wet basis, a 20 mL aliquot was taken in a porcelain cap and 5 g of montmorillonite K 10 was added with stirring manual.
- the starch gel, prepared as in Example 2 was added into and manually agitated with the spatula. The remaining montmorillonite was added in portions of 8 to 10 times. The mixture was homogenized by stirring with a spatula until the mixture was observed without moisture.
- the paste was extruded; the extrudates were dried at room temperature for 18 h, fragmented into sizes 3-4 cm in length, placed in a porcelain cap of 12 cm in diameter, dried at 120° C for 3 h, and calcined at 350° C for 4 h.
- the calcined extrudates were crushed and sieved to obtain particles sizes between 30-40 mesh for its evaluation in a bench reactor; the loaded density was 0.8991 g/cm 3 .
- the extrudate catalyst prepared with metal/P weight ratio, on wet basis, of 0.2 Li/P, 0.06 AL/P and Ti/P of 0.05 was named as HLPAT-1 and it showed the following properties: surface area of 94.8 m 2 /g, pore volume of 0.15 cm 3 /g and average pore diameter of 62.7 ⁇ .
- the mixture was homogenized and then dried with a cold air gun for 1 h to remove excess moisture from the pasta, the pasta was allowed to age for 12 h to obtain a paste of suitable consistency to extrude.
- the extrudates were placed in stainless steel trays, dried at room temperature for 18 h, fragmented into 3-4 cm lengths, placed in a porcelain cap, dried at 120° C for 3 h, and calcined at 480° C for 4 h; then they were crushed and sieved through mesh numbers 30 and 40. The density was determined using the particles retained in the 40 mesh, which was 0.7300 g/cm 3 .
- the catalyst had a metal/P weight ratio of 1.19 Li/P, 4.6 AL/P and Mg/P of 2.1, and was named as HLPAM-3. It showed the following properties: surface area of 52.1 m 2 /g, pore volume of 0.20 cm 3 /g and average pore diameter of 153.8 ⁇ .
- the extrudate catalyst prepared with metal/P weight ratio on wet basis of 0.08 Li/S and 0.32 AL/S was named as HLSA-4, and it showed the following properties: surface area of 127 m 2 /g, pore volume of 0.26 cm 3 /g and average pore diameter of 83.4 ⁇ .
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nanotechnology (AREA)
Abstract
The catalysts are prepared from a hydrogel or dispersion of lithium aluminum hydroxides in water and oxygenated solvent, which comes from the hydrolysis of aluminum lithium hydride with water and oxygenated solvent, such as an ether.
The catalysts may be used in batch reactor and continuous flow systems as a promoter of reactions that require moderate Lewis acidity. Application example is in the transesterification reaction of vegetable oils and/or animal fat to produce biodiesel.
Description
- The present invention relates to:
- novel heterogeneous acid catalysts consisting of mixed metal salts, such as lithium and aluminum phosphates and sulfates and their combinations with metallic cations, such as magnesium, titanium, zinc, zirconium and gallium, which provide Lewis acidity; organic or inorganic porosity promoters, such as polysaccharides and agglomerates, such as clays, kaolin and metal oxides of the type MxOy, where M = Al, Mg, Sr, Zr or Ti, among other metals of groups IA, IIA and IVB, x = 1 or 2 and y = 2 or 3, for the formation of particles with geometry and established size, such as extrudates, spheres, trilobes and raschig rings, among others;
- the process to obtain heterogeneous acid catalysts from a hydrogel or dispersion of lithium aluminum hydroxides in water and a oxygenated solvent, in which the hydrogel or dispersion is prepared from the hydrolysis of aluminum lithium hydride with water and a oxygenated solvent, such as an ether; and
- the utilization of heterogeneous acid catalysts as a promoter of reactions that require moderate Lewis acidity in batch and continuous flow systems in various industries, such as petroleum refining, petrochemical and general chemistry. An application example is in the transesterification reaction of vegetable oils and / or animal fat to produce biodiesel, but its use is not limited to the production of this biofuel.
- In the article Advances in Heterogeneous Catalysis for Biodiesel Synthesis, Top Catal. 53, 721-736, 2010, Yan et al. describe both the limitations of homogeneous or first generation catalysts which act in the same reaction phase as the advantages of heterogeneous or second generation catalysts for the synthesis of biodiesel.
- The limitations of the homogenous catalysts or so called "first generation" are:
- a) their use is normally restricted to batch processing, and are primarily highly corrosive acids or bases.
- b) the stages of the homogeneous biodiesel production process require long times and the processing is costly because of needed the steps such as: oil pretreatment, catalytic transesterification, fatty acid methyl ester (FAME) separation from glycerin, neutralization of the residues from the homogeneous catalyst, methanol distillation, washing of the FAME phase with water, and vacuum drying of the desired products.
- c) it is impossible to reuse the homogeneous catalyst in reaction in new cycles because of its lost in the waste streams.
- d) separation of the products requires a post-treatment with large volumes of water to neutralize the catalyst residues which generates waste water that must be treated before its disposal into the environment; and
- e) the homogeneous catalyst is sensitive to free fatty acids (FFA) and water present in vegetable oils.
- The advantages of heterogeneous catalysts or so-called "second-generation" are:
- a) the catalyst is not lost during the reaction and can be recovered from the reaction medium and reused to several reaction cycles;
- b) the performance in fixed bed reactors for continuous flow processes;
- c) the post-treatment of product is not required, greatly reducing the ecological impact by avoiding the liquid wastes generated during the purification of the products; and
- d) the microcrystalline structure in the catalyst surface is stable, which extends its useful life
- Some investigations have been focused on the study of transesterification basic catalysts in low-acid vegetable oils such as Jatropha oil and sunflower with high yields of biodiesel at non-severe reaction conditions. On the other hand, acidic catalysts are strongly recommended for use in the esterification and / or transesterification of vegetable oils with a higher degree of acidity and of animal fats, together with alkaline catalysts under conditions of moderate to high severity. Acid catalysts may be defined as oxygen carbonyl activators of the ester to increase its reactivity to the attack of the alcohol, typically methanol. These acid catalysts can be classified in those with Brönsted acid sites because they have carbonyl oxygen interactions with catalytic proton (H+) sites and those with Lewis acid sites because of interactions of carbonyl oxygen with cationic (M+) sites in the catalyst.
-
Figure 1 describes the above explained, emphasizing experimental evidence showing the type of acidity on the surface of the catalyst by pyridine adsorption measured on an infrared spectrum which describes the interaction of a Lewis base on an acid surface. The interaction of the acidic sites on the surface with the pyridine molecule generates different bands. The characteristics for Brönsted acid sites appear at 1,545 cm-1 and the characteristics for Lewis acid sites appear at 1,445 cm-1 and the intermediate band at 1,490 cm-1 for the two interactions: - Section (a) of
Figure 1 shows how the acid catalyst with Brönsted (H+) sites acts on the triglyceride molecule by activating it for the transesterification reaction; - in section (b) of
Figure 1 illustrates how the acid catalyst with Lewis (M+) sites acts on the triglyceride molecule by activating it for the transesterification reaction; - a catalyst having both types of sites is presented in section (c) of
Figure 1 . - These interactions are also present in diglycerides and monoglycerides by activating themselves for transesterification reactions with an alcohol, such as methanol. Thus, we can say that the catalysts of acidic nature to activate either the triglyceride, diglyceride or monoglyceride molecule, act as the promoter of the C = O ester.
- Catalysts with Brönsted acidity, such as heteropolyacids (HPAs), have shown high catalytic activity, yield and conversion, in combination with monovalent cations, such as Cs+. HPAs based on Nb and W supported on W-Nb, tungstated zirconia, tantalum and silver pentoxide have shown greater resistance to catalyst leaching, as described in the following bibliographic citations.
- Katada N. et al., in Applied Catalysis A General, (2009), 363 (164: 168) have studied solid acid catalysts derived from heteropolyacids (HPAs) with W and Nb. They found that under a calcination temperature of 773°K, W and Nb-based HPAs are supported on WO3-Niobia (WO3-Nb2O5) and are transformed into insoluble NPNbW / W-Nb formulations in the reaction mixture with high catalytic activity for the transesterification of triolein and ethanol to ethyloleate. The reaction rate is increased when methanol is used instead of ethanol. Due to the potential and catalytic stability during at least 4 days of reaction of these catalysts, the authors recommend carrying out the reaction in fixed bed and continuous flow reaction systems.
- Shi et al., in Chemical Engineering & Technology (2012), 35 (2), 347-352 disclose that heteropolyacids (HPAs) were used as triglyceride transesterification catalysts, arguing both Brönsted and Lewis acidity properties. HPAs that are strong Brönsted acids, depending on their composition and the reaction medium, possess good thermal stability, high acidity and high oxidizing capacity and are water tolerant. Among HPAs, 12-tungstophosphoric acid (H3PW12O40) is chosen because of its high activity since it shows a Keggin structure which is composed of a coordinated tetrahedral heteroatom of oxygen (PO4) surrounded by 12 additions of atoms sharing coordinated octahedral oxygen atoms (WO6) according to Oliveira CF et al. in Esterification of oleic acid with ethanol by 12-tungstophosphoric acid supported on zirconia. Appl Catal A-Gen 372: 153-161 (2010).
- Heterogeneous catalysts of acidic nature such as those based on sulfated zirconia have been reported, in which it emphasized the fact that the carbonyl oxygen is activating by acid sites of Brönsted nature according to Rattanaphra et al., "Simultaneous Conversion of Triglyceride / Free Fatty Acid Mixtures into Biodiesel Using Sulfated Zirconia ", Top Catal. 53: 773-782, 2010.
- On the other hand, the esterification of palmitic acid with HPA catalyst was also carried out by Caetano et al. "Esterification of free fatty acids with methanol using heteropolyacids immobilized on silica. Catal Commun 9:1996-1999 (2008), using heterogeneous catalysts: Tungstophosphoric acid (PW), molybdophosphoric acid (PMo), and immobilized tungstosilicic acid (SiW) on silica by the sol-gel technique; from these prototypes the PW proved to be the best catalyst so it was studied with different concentrations of silica, obtaining 100% conversion of palmitic acid with a concentration of 0.042 g PW / g silica.
- Alternatively, in the patent document reported by
Tian et al., CN 103801282 , "Solid base catalyst, and preparation method and application thereof", the use of an aluminum-Zn spinel catalyst (ZnAlxO1 + 1.5x in which x = 1.5-2.5) doped with La is described. The basic solid catalyst is used in the transesterification reaction of fatty acid esters with an alcohol to produce biodiesel; it is highly active and stable during the utilization, the active components are not lost. - In the patent document
CN 103,752,297 "Zirconium-oxide catalyst for producing biodiesel, as well as preparation method and application of zirconium-oxide catalyst. 2014 "a zirconium oxide catalyst is claimed to produce biodiesel in a tubular reactor at a reaction temperature of 250-300° C, reaction pressure of 7 to 14 MPa and volume ratio of alcohol-oil of 0.5: 1 to 7 :1. The catalyst is characterized by containing zirconium oxide of 80-95 weight %, aluminum oxide of 2-18 weight %, 1 to 17% titanium dioxide, 5 to 25% sodium bicarbonate and 10 to 50 % of sodium chloride and in the patent documentCN 103,706,384 "Preparation method of bio-diesel catalyst" (2014), there is provided a method of preparing a catalyst for the production of biodiesel in a continuous flow process in which the composition is PO4 3- / ZrO2 doped with rare earth metals such as La, Ce, Pr, Nd, etc. - The French Institute of Petroleum has developed an industrial technology called Esterfip-H ™, which refers to a continuous process of transesterification where the reaction is promoted by a heterogeneous catalyst, which is a zinc aluminate (ZnAl2O4) spinel, which promotes the transesterification reaction, without loss of catalyst. The reaction is carried out at an operating temperature of 180-220° C and pressure of 40-60 bar. The yields obtained are greater than 98%, with an excess of methanol. However, the raw material must have a free fatty acid content of less than 0.25% and a water content of less than 1,000 ppm. (Juan A. Melero et al., Critical Review, Heterogeneous acid catalysts for biodiesel production: current status and future challenges, Green Chem., 2009, 11, 1285-1308.)
- In the patent document
US Pat. No. 5,908,946 (Stern R. et al., Inst. Frangais du Petrole, Process for the production of esters from vegetable oils or animal oils alcohols, 1999), for the production of esters of linear monocarboxylic acids with oils of 6 to 26 vegetable carbon atoms or oils of animal origin are reacted with monoalcohols having a low molecular weight, for example 1 to 5 carbon atoms, in the presence of a catalyst selected from zinc oxide, mixtures of zinc oxide and aluminum oxide, and the zinc aluminates corresponding to the formula: ZnAl2 O4, x ZnO, and Al2O3 (with x and y being 0-2) and with a spinel-like structure, allowing the direct production in one or more steps, of an ester which can be used as fuel and pure glycerin. In order to process vegetable oil, severe operating conditions, temperatures of 170-250° C, pressures lower than 100 bar, with excess of the stoichiometric alcohol are considered, obtaining conversions of 80-85%, in the case of acid oil charges conditions are used operating conditions of 180-220° C, with pressures less than 1 bar. - Considering metal phosphates as metal catalysts for transesterification of biodiesel, Xie et al., in Bioresource Technology (2012), 119, 60-65, describe acid catalysts for transesterification of triglyceride esters based on 30 wt% WO3 supported in AlPO4 which were tested in batch reaction systems at 180° C for 5 h and a methanol / oil ratio of 30: 1 at a dose of 5% by weight catalyst.
- Other transesterification catalysis systems consist of calcium phosphates from animal bone pyrolysis, which generates hydroxyapatite at 800° C as described by Obadiah et al., in Bioresource Technology (2012), 116, 512-516.
- Similarly, in the patent document
CN 103,484,258 "Method for preparing biodiesel by using nano hydroxyapatite to catalyze triglyceride 2014", a method is described for preparing biodiesel in the presence of a nanohydroxyapatite catalyst using from 0.5 to 3 weight % and operating at 800 to 300° C for 2 to 10 h. - Yin et al. describe in Fuel (2012), 93, 284-287 the catalytic activity of K3PO4 at conditions of 220° C, a methanol-oil ratio of 24: 1 and 1% of the catalyst resulting in a conversion of 95.6%.
- Sodium phosphate has also been used as a transesterification catalyst for triglyceride esters in biodiesel production according to De Filippis et al., in Energy & Fuels (2005), 19 (6), 2225-2228
- Hitherto, no lithium and aluminum phosphates and sulphates have been considered, in addition to their combinations with metallic cations, such as magnesium, titanium, zinc, zirconium and gallium, as heterogeneous phase catalysts with a Lewis nature both in reaction systems by batch and in continuous flow reaction systems. Neither has the synthesis of the same catalyst from hydrolysis products of lithium aluminum hydride and these hydrolysis products been considered as the source of lithium and aluminum for the formation of phosphates and sulphates from the reaction with the corresponding acid (Phosphoric acid or sulfuric acid), and other sources of metals such as magnesium, titanium, zinc, zirconium and gallium, from metal acetates.
- It is therefore an object of the present invention the synthesis of solid catalysts with Lewis acid sites, wherein the catalyst uses in its composition mixed metal salts, such as lithium and aluminum phosphates and sulfates, in addition to their combinations with metal cations such as magnesium, titanium, zinc, zirconium and gallium.
- Another object of the present invention is that the precursor of the mixed metal salts, such as lithium and aluminum phosphates and sulfates, in addition to their combinations with metal cations such as magnesium, titanium, zinc, zirconium and gallium, come from a material product of the addition of water and oxygenated solvent, such as an ether, preferably tetrahydrofuran, diethyl ether or dimethoxyethane, on aluminum lithium hydride at temperatures of -20 to 60° C with stirring from 0-10,000 rpm , generating a dispersion of hydroxides of lithium and aluminum in water and oxygenated solvent, with a pH of 10 to 16, according to the reaction (1):
LiAlH4 + 4 H2O → LiOH + Al(OH)3 + 4 H2 (1)
- Another object of the present invention is that the catalyst is obtained from the addition of phosphoric acid or sulfuric acid to the mixture of lithium and aluminum hydroxides, product of the hydrolysis of lithium aluminum hydride (reaction 1), to obtain compositions of lithium: aluminum, phosphorous or sulfur and the incorporation of metals such as titanium and magnesium as promoters of Lewis acid sites from their acetic acid salts
- A further object of these catalysts is that in their composition binders, such as clays, kaolin and metal oxides of the MxOy type, are added, where M = Al, Mg, Sr, Zr or Ti, among other metals of groups IA, IIA and IVB, x = 1 or 2 and y = 2 or 3, for the formation of particles of shape and size, such as extrudates; and organic or inorganic porosity promoters of the catalyst, such as polysaccharides.
- An additional object of these catalysts is their use in batch and continuous flow systems as promoters of reactions that require moderate Lewis acidity in various industries, such as petroleum refining, petrochemical and general chemistry.
- The foregoing and further objects of the present invention will be established more clearly and in detail in the following sections.
-
-
Figure 1 . Scheme showing the classification of acid catalysts according to Brönsted acid sites by having interactions of carbonyl oxygen with catalyst (H +) proton (H +) sites and those with Lewis acid sites due to interactions of oxygen Carbonyl with the cationic sites (M +). -
Figure 2 . Flow chart for the preparation of heterogeneous acid catalysts based on mixed metal salts of the present invention. -
Figure 3 . Scheme showing the Lewis acidity sites of the mixed metal salt heterogeneous catalysts of the present invention, HLPA, HLPAT and HLPAM series determined by Fourier Transform Infrared Spectrometry (FTIR). - The present invention relates to:
- novel heterogeneous acid catalysts consisting of mixed metal salts, such as lithium and aluminum phosphates and sulfates. In addition, to their combinations with metallic cations, such as magnesium, titanium, zinc, zirconium and gallium, which provide adequate Lewis acidity; organic or inorganic porosity promoters, such as polysaccharides; and agglomerates, such as clays, kaolin and metal oxides of the type MxOy, where M=Al, Mg, Sr, Zr or Ti, among other metals of groups IA, IIA and IVB, x=1 or 2 and y=2 or 3, for the formation of particles with geometry and established size, such as extrudates, spheres, trilobes and raschig rings, among others;
- the process of obtaining them from a hydrogel or dispersion of lithium aluminum hydroxides in water and oxygenated solvent, which comes from the hydrolysis of aluminum lithium hydride with water and oxygenated solvent, such as an ether; and
- its use in batch and continuous flow systems as a promoter of reactions that require moderate Lewis acidity in various industries, such as refining, petrochemical and general chemistry.
-
Figure 2 shows in general terms the flow diagram by which some of the heterogeneous acid catalysts preferred by the present invention are obtained: - Lithium and aluminum phosphates (HLPA series),
- Lithium, aluminum and titanium phosphates (HLPAT series),
- Lithium, aluminum and magnesium phosphates (HLPAM series), and
- Lithium and aluminum sulfates (HLSA series).
- The preparation of these catalysts consists of having a source of lithium and aluminum, such as the mixture of lithium and aluminum hydroxides or lithium aluminate, which are generated by the reaction of lithium aluminum hydride with water, forming a large quantity of hydrogen and the products described in reaction (1):
LiAlH4 + 4 H2O → LiOH + Al(OH)3 + 4 H2 (1)
- The reaction (1) is highly exothermic (ΔH°298 = -714 kJ/mol). It is also reported in the literature, (BB Baker, WM MacNevin, "Lithium Aluminum Hydride as Reagent for Determination of Water" Anal. Chem. 22: 364-365, 1950), that there is a possibility that the following reactions occur, an acid aluminate (reaction 2) or an aluminate as such (reaction 3).
2 LiAlH4 + 8 H2O → 2 LiOH + 2 Al(OH)3 + 8 H2 (1)
LiOH + 2 Al(OH)3 → LiH(AlO2)2 + 3 H2O (2)
or
LiAlH4 + 2 H2O → LiAlO2 + 4 H2 (3)
- On the other hand, the lithium aluminate is formed by dissolving aluminum in lithium hydroxide, as a white precipitate, which by calcination generates 2Al2O3-Li2O (Horan HA, Damiano JB "The Formation and Composition of Lithium Aluminate" J. Am. Chem. Soc., 57: 2434-2436, 1935).
- The mixture of lithium and aluminum hydroxides, prepared above, is reacted with phosphoric acid or sulfuric acid at different concentrations to obtain lithium and aluminum phosphates or sulfates; in the reaction (4) is used phosphoric acid, and in the reaction (5) sulfuric acid is used to show these reactions:
4 LiOH + 2 Al(OH)3 + 4 H3PO4 → Li4Al2P4O15 + 11 H2O (4)
4 LiOH + 2 Al(OH)3 + 4 H2SO4 → Li4Al2S4O17 + 9 H2O (5)
- These aqueous dispersions are formulated with organic or inorganic porosity promoters, such as polysaccharides, and binders such as clays, kaolin and metal oxides of the MxOy type, where M = Al, Mg, Sr, Zr or Ti, among others, x = 1 or 2 and y = 2 or 3, for the formation of particles with geometry and size, such as extrudates, spheres, trilobes and raschig rings, among others; subsequently, by the extrusion, drying and calcination steps, the catalysts are produced with a formulation of Li-Al-P or Li-Al-S with Lewis type acidic nature. According to
Figure 2 the flow chart shows the procedure for the preparation of the catalysts labeled HLPA and HLSA. However, it is feasible for the lithium and aluminum phosphates and/or sulfates to incorporate another Lewis acidity promoting cation such as titanium or magnesium, by means of a solution of titanium acetate or magnesium by a mixing step with agitation for 2-8 hours, preferably 2-3 hours. - In this regard, it is important to note that titanium and magnesium acetates are preferably prepared from the corresponding titanium and magnesium alkoxides, for example titanium isopropoxide or magnesium ethoxide; these alkoxides react with glacial acetic acid in stoichiometric proportions according to reactions (6) and (7):
[(CH3)2CHO]4Ti + 4 CH3COOH → (CH3COO)4Ti + 4 (CH3)2CHOH (6)
[CH3CH2O]2Mg + 2 CH3COOH → (CH3COO)2Mg + 2 CH3CH2OH (7)
- The mixture obtained from the reaction with the titanium and magnesium salt generates precursors of the Li-P-Al-Ti, Li-P-Al-Mg, Li-S-Al-Ti and Li-S-Al-Mg respectively, that is formulated with porosity promoters, such as polysaccharides; and agglomerates, such as clays, kaolin and metal oxides of the type MxOy, in which M = Al, Mg, Sr, Zr or Ti, among other metals of groups IA, IIA and IVB, x = 1 or 2 and y = 2 or 3 for obtaining particles with geometry and established size, such as extrudates, spheres, trilobes and raschig rings, among others; the catalysts with a formulation of Li-P-Al-Ti, Li-P-Al-Mg, Li-S-Al-Ti and Li-S-Al-Ti are produced by extrusion, drying and calcination stages. Mg, respectively, with Lewis type acidic nature. According to
Figure 2 , the flow chart shows the formulation of the catalysts, which are described as HLPAT, HLPAM, HLSAT and HLSAM respectively. - In this regard, a graph in
Figure 3 shows the Lewis acidity sites of the mixed metal salts heterogeneous acid catalysts of the present invention, HLPA, HLPAT and HLPAM series, respectively, as determined by Fourier Transform Infrared Spectrometry (FTIR). - The process of obtaining the heterogeneous acid catalysts of the present invention comprises the following steps:
- a) obtaining a hydrogel from the aluminum hydrolysis of lithium hydride: preparation of the reaction system for the addition of water and oxygenated solvent, such as an ether, to lithium aluminum hydride under an inert atmosphere, at a temperature of -20 to 60° C and stirring from 0 to 10,000 rpm, generating a dispersion of lithium aluminum hydroxides in water and oxygenated solvent, with a pH of 10 to 16;
- b) the hydrogel or dispersion of lithium aluminum hydroxides in water and oxygenated solvent obtained in step a) is reacted with the corresponding acid to obtain the mixed metal salt, preferably lithium aluminum phosphate or sulfate, in the quantity necessary for the concentration of phosphorus or sulfur to be established;
- c) the suspension obtained in step b) is homogenized by stirring until having a crystalline solution;
- d) to the crystalline solution obtained in step c) is added the acetate solution corresponding to the metal cation to be integrated into the mixed metal salt of lithium and aluminum, such as magnesium, titanium, zinc, zirconium or gallium acetate, maintaining stirring for 2 to 8 hours to homogenize;
- e) an organic or inorganic porosity promoter, such as a polysaccharide, is added to the homogenized solution obtained in step d), while agitation is maintained until homogenized;
- f) to the homogenized solution obtained in step e) is added a binder, such as clay, kaolin or metal oxide of the type MxOy, where M=Al, Mg, Sr, Zr or Ti, among other metals of the groups IA, IIA and IVB, x=1 or 2 and y=2 or 3, maintaining agitation until homogenization and subsequent aging and drying of the paste; and
- g) the obtained paste in step f) is extruded; the extrudates are dried at room temperature for 16 to 20 hours; are fragmented to the desired size, preferably 3 to 4 cm in length; dried at 100-140° C for 2 to 4 hours; are calcined at 250-500° C for 2 to 4 hours; and finally they are crushed and sieved.
- the water used in step a) is preferably deionized water;
- the oxygenated solvent employed in step a) is preferably an ether, such as tetrahydrofuran, diethyl ether or dimethoxyethane;
- the ether used as the oxygenated solvent in step a) is preferably anhydrous tetrahydrofuran (THF);
- the addition of water and oxygenated solvent in step a) is carried out as a pre-prepared mixture in a volume ratio of 5: 1 to 1: 5, preferably at a rate of 1 drop per second;
- the volume ratio of water to the aluminum lithium hydride used in step a) is 3 to 20 parts of water per mole of lithium aluminum hydride;
- the inert atmosphere in step a) is preferably generated using nitrogen gas (N2), argon or helium;
- the temperature used in step a) is preferably 0 to 5° C;
- the corresponding acid employed in step b) is preferably added at a rate of 1 drop per second;
- the solution of the acetate to be added in step d) corresponding to the metal cation to be integrated into the mixed metal salt of lithium and aluminum is prepared just prior to use by reacting the alcohol, such as isopropoxide or ethoxide with acid acetic acid while maintaining stirring for 2 to 6 hours;
- the acetates preferably used in step d) are magnesium acetate and titanium acetate;
- the agitation employed in step d) to homogenize preferably is maintained for 2 to 3 hours;
- the polysaccharide used as the porosity promoter in step e) is preferably amylose-amylopectin (starch);
- the clay used as a binder in step f) is preferably of the montmorillonite, kaolin, silica or alumina type;
- the mixed metal salts besides their combinations with metallic cations preferably obtained are:
- Lithium and aluminum phosphates and sulfates (HLPA and HLSA series respectively),
- Lithium, aluminum and titanium phosphates and sulfates (HLPAT and HLSAT series respectively), and
- Phosphates and sulfates of lithium, aluminum and magnesium (HLPAM and HLSAM series respectively); and
- the process of obtaining lithium and aluminum phosphates and sulfates (HLPA and HLSA series respectively) does not comprise step d).
- The heterogeneous acid catalysts preferred by the present invention are preferably composed of mixed metal salts such as lithium and aluminum phosphates and sulfates with the following percentages of metals by weight of the catalyst: lithium from 0 to 5 weight %, preferably from 0.1 to 3 weight %, and aluminum from 0 to 15 weight %, preferably from 0.3 to 10 weight %; in addition to their combinations with metal cations in concentrations of 0 to 40 weight % of the catalyst, preferably 0.2 to 30 weight %, such as magnesium, titanium, zinc, zirconium, gallium and silicon, which provide suitable Lewis acidity; organic or inorganic porosity promoters in concentrations of from 0.05 to 25 weight % of the wet base catalyst, preferably from 0 to 12 weight %, such as polysaccharides; and binders in concentrations of 1 to 20 weight % of the catalyst, preferably 3 to 15 weight %, such as clays, kaolin and metal oxides of the MxOy type, where M = Al, Mg, Sr, Zr or Ti, among other metals of The groups IA, IIA and IVB, x = 1 or 2 and y = 2 or 3, for the formation of particles with geometry and established size, such as extrudates, spheres, trilobes and raschig rings, among others; having the following properties: surface area of 10 to 180 m2/g, preferably 30 to 80 m2 /g, pore volume of 0.1 to 0.5 cm3/g, preferably 0.1 to 0.3 cm3/g, and average pore diameter 100 to 200 Å, preferably 110 to 170 Å.
- The physico-chemical properties of the heterogeneous acid catalysts of the present invention allow their use in batch reaction and continuous flow systems as promoters of reactions which require moderate Lewis acidity in various industries, such as petroleum refining, petrochemical and chemical.
- Some practical examples of the present invention are described for a better understanding thereof, without limiting its scope.
- Example 1 describes the typical preparation of the lithium-aluminum hydroxide dispersion from the reaction of water with the aluminum lithium hydride;
- Example 2 describes the reaction of phosphoric acid with the dispersion of lithium and aluminum hydroxides to generate the lithium and aluminum phosphates, which are precursors of HLPA series catalysts;
- Examples 3 and 4 describe processes for incorporating lithium and aluminum phosphates, titanium and magnesium metals respectively (HLPAT and HLPAM series catalysts, respectively), starting from the corresponding acetate, and the method of preparing such acetates; y
- Example 5 describes the preparation of heterogeneous acid catalysts based on lithium aluminum sulfates (HLSA Series).
- A magnetic stirrer was placed in a 500 mL three-necked round flask with 24/40 outlet. The flask was previously washed, rinsed with acetone and deionized water and dried into oven at 115° C for 24 h. A refrigerant was connected to the mouth central portion of the flask, having at the upper end a stopper (septa), in which a needle and a balloon filled with nitrogen gas (N2) was inserted in order to generate an inert atmosphere in the system. In one of the side mouth of the flask, an addition funnel was placed using a glass stopper; in the other mouth of the flask a purge or vent plug was placed. The flask was placed in an ice bath with methanol and NaCl to avoid heating because of the exothermic reaction. Similarly, the arrangement of an inert atmosphere in the system was ensured by passing the nitrogen gas stream (N2) contained in the balloon. 70 mL of freshly distilled anhydrous ether tetrahydrofuran (THF) was added to the flask thru the addition funnel; then agitation commenced. 14.3 g of lithium aluminum hydride (LAH) was placed in a 125 ml wide-mouth amber bottle with screw cap and inert atmosphere (nitrogen stream), previously dried at 120° C for 2 hours. Then, small portions (7 to 10 time) of anhydrous THF were added in the bottle aided by a plastic funnel. The stream nitrogen and stirring was maintained. Because it is an exothermic reaction, it is extremely important to ensure that the amount of ice is sufficient to cool the flask. CAUTION! BE CAREFUL THAT THE LAH POWDER DOES NOT FALL TO THE ICE BATH, because the reaction is very violent. The funnel and the flask walls were washed with 50 mL of anhydrous THF, dosed with a Pasteur pipette. Finally, the funnel was removed and the purge or vent plug was placed in its place. Sufficient ice was added to the vessel to cover the flask and maintain the temperature at 0-5° C. A mixture of deionized water:THF, in a volume ratio of 4: 3, was prepared in a 100 mL graduated cylinder and placed in the addition funnel, located in one of the mouths of the flask, ensuring that the stopcock was closed. The addition of the deionized water:THF mixture was started at a rate of 1 drop per second (¡CAUTION! HYDROGEN, H2, IS GENERATED). A white suspension was obtained in the first drop of the addition. The bath was maintained with sufficient ice and the continuous flow of N2 through the system, allowing the gas mixture (H2-N2) exiting the purge to be drawn towards the hood. Stirring was maintained at speeds lower than 1 RPM. At the end of the addition of the deionized water:THF mixture, the deionized water was added to the addition funnel and added to the LAH by dropping the amount and time shown in Table No. 1. It is important to emphasize that the addition of water must be slow, because it is an exothermic reaction and H2 is generated.
Table No. 1. Addition of deionized water to aluminum lithium hydride (LAH). Addition number Deionized water Volume (mL) Addition time (min) 1 50 60 2 50 30 3 50 20 4 10 10 - As the reaction progressed, the gray particles disappeared and the appearance of the reaction mixture turned white. At the end of the reaction, it was ensured that there was no LAH (dark gray) to continue the reaction, and then the refrigerant was removed as well as the addition funnel and the vent. The mixture obtained was a white dispersion of lithium and aluminum hydroxides in water and tetrahydrofuran, with a pH of 14, which was stored in a wide-mouth bottle, tightly closed and sealed for later use.
- Ortho-phosphoric acid was slowly added dropwise in a 100-mL beaker containing 20 g of the lithium aluminum hydroxide dispersion in water and tetrahydrofuran obtained in Example 1, the amount of the ortho-phosphoric acid was the necessary for having a concentration of 0.55% of P, on wet basis. The suspension was homogenized, first with a spatula and then with a magnetic stirrer to have a crystalline solution, then 4 g of the starch gel was prepared and added. The preparation of the starch gel was as follows: to 1 g of starch contained in a glass beaker, 30 mL of deionized water was added; the mixture was heated at 70° C for 30 min and taken to room temperature.
- After adding the starch gel, 8.5 g of montmorillonite K 10 were added with manual stirring in portions of 8-10 fold. The mixture was stirred with a spatula until completely homogeneous and with little moisture. The paste was extruded and the extrudates were put in stainless steel trays to allow them to dry at room temperature for 18 h. Subsequently, the extrudates were fragmented to sizes of 3-4 cm in length and placed in a porcelain cap of 12 cm in diameter to be dried at 120° C for 3 h; then, they were calcined at 350° C for 4 h. Finally, the calcined extrudates were crushed and sieved for obtaining between 30 to 40 mesh (0.42 to 0.59 mm) particle sizes. The loaded density of the particles that are retained in the 40 mesh is determined for evaluation in a bank reactor, which is 0.5241 g/cm3.
- The extruded catalyst prepared with metal/P weight ratio, on wet basis, of 1.2 Li/P and 4.7 AL/P was named as HLPA-16 heaving the following properties: surface area of 137 m2/g, pore volume of 0.25 cm3/g and average pore diameter of 73.4 Å.
- For the preparation of this series of catalysts, it is necessary to maintain stable titanium avoiding the hydrolysis, for it is required to have a solution of titanium acetate since it is more stable than an alkoxide.
- 4 g of titanium isopropoxide was weighed into a 100 mL beaker and 16 g of glacial acetic acid was added while maintaining magnetic stirring for 10 min to obtain a crystalline solution. The reaction was carried out as follows:
[(CH3)2CHO]4Ti + 4 CH3COOH → (CH3COO)4Ti+ 4 (CH3)2CHOH
- Catalyst. 20 g of the dispersion of lithium aluminum hydroxide in water and tetrahydrofuran obtained in Example 1, were weighed into a 100 mL beaker, and 3.8 mL of ortho-phosphoric acid was slowly added into dropwise.
- The suspension was homogenized with stirring and the previously prepared crystalline solution of titanium acetate was added. While maintaining continuous stirring, more orthophosphoric acid was added into dropwise to obtain a phosphorus concentration of 4.2 wt % on wet basis, a 20 mL aliquot was taken in a porcelain cap and 5 g of montmorillonite K 10 was added with stirring manual. The starch gel, prepared as in Example 2, was added into and manually agitated with the spatula. The remaining montmorillonite was added in portions of 8 to 10 times. The mixture was homogenized by stirring with a spatula until the mixture was observed without moisture.
- The paste was extruded; the extrudates were dried at room temperature for 18 h, fragmented into sizes 3-4 cm in length, placed in a porcelain cap of 12 cm in diameter, dried at 120° C for 3 h, and calcined at 350° C for 4 h. The calcined extrudates were crushed and sieved to obtain particles sizes between 30-40 mesh for its evaluation in a bench reactor; the loaded density was 0.8991 g/cm3.
- The extrudate catalyst prepared with metal/P weight ratio, on wet basis, of 0.2 Li/P, 0.06 AL/P and Ti/P of 0.05 was named as HLPAT-1 and it showed the following properties: surface area of 94.8 m2/g, pore volume of 0.15 cm3/g and average pore diameter of 62.7 Å.
- For the synthesis of this series of catalysts, it is necessary to prepare a solution of magnesium acetate.
- 1.6 g of magnesium ethoxide were weighed into a 100 mL beaker, and 10 g of glacial acetic acid were added to the flask standing in an extractor hood. The magnetic stirring was maintained for 3 h to obtain an amber solution. The reaction was carried out as follows:
[CH3CH2O]2Mg + 2 CH3COOH → (CH3COO)2Mg+ 2 CH3CH2OH
- Catalyst. Into a 100 mL beaker, 20 g of the lithium aluminum hydroxide dispersion in water and tetrahydrofuran obtained in Example 1 were weighed and 0.4 mL of orthophosphoric acid was slowly added dropwise to obtain a phosphorus concentration of 0.8 wt.%. The slurry was homogenized with a spatula; then, the magnesium acetate solution in the form of prepared lumps was added maintaining the stirring for 3 h to homogenize and obtain a yellow solution. 4 g of the starch gel, prepared as in Example 2, was homogenized and 20 g of montmorillonite K 10 was added stirring with a spatula. The mixture was homogenized and then dried with a cold air gun for 1 h to remove excess moisture from the pasta, the pasta was allowed to age for 12 h to obtain a paste of suitable consistency to extrude. The extrudates were placed in stainless steel trays, dried at room temperature for 18 h, fragmented into 3-4 cm lengths, placed in a porcelain cap, dried at 120° C for 3 h, and calcined at 480° C for 4 h; then they were crushed and sieved through mesh numbers 30 and 40. The density was determined using the particles retained in the 40 mesh, which was 0.7300 g/cm3.
- The catalyst had a metal/P weight ratio of 1.19 Li/P, 4.6 AL/P and Mg/P of 2.1, and was named as HLPAM-3. It showed the following properties: surface area of 52.1 m2/g, pore volume of 0.20 cm3/g and average pore diameter of 153.8 Å.
- In a 100 mL beaker containing 20 g a dispersion of the lithium aluminum hydroxide in water and tetrahydrofuran, obtained in Example 1, sulfuric acid was slowly added dropwise in the amount necessary for the S concentration of 3.4% wet basis. The suspension was stirred and homogenized with a spatula and then, it was stirred with the aid of a magnetic stirrer to provide a crystalline solution. 4.4 g of the starch gel was added to the solution; the gel starch was prepared as follows: to 1 g of starch contained in a glass flask, 30 mL of deionized water was added, the mixture was heated to 70° C for 30 min and allowed to cool to room temperature.
- After the starch gel was added, 12.5 g of montmorillonite K 10 were added with manual stirring in 8-10 fold portions. The mixture was stirred with a spatula until completely homogeneous and the mixture was observed with little moisture. The paste was extruded, and the extrudates were placed in stainless steel trays to allow them to dry at room temperature for 18 h. Subsequently, the extrudates were fragmented to 3-4 cm sizes in length, and placed in a porcelain cap of 12 cm in diameter to be dried at 120° C for 3 h and calcined at 350° C for 4 h; at the end, they were crushed and sieved to obtain particle sizes between 30 to 40 mesh (0.42 to 0.59 mm). The compact density of the particles retained in the 40 mesh was determined for evaluation in a bench reactor, which was 0.6973 g/cm3.
- The extrudate catalyst prepared with metal/P weight ratio on wet basis of 0.08 Li/S and 0.32 AL/S was named as HLSA-4, and it showed the following properties: surface area of 127 m2/g, pore volume of 0.26 cm3/g and average pore diameter of 83.4 Å.
Claims (23)
- Heterogeneous acid catalysts consisting of mixed metal salts such as lithium and aluminum phosphates and sulfates with the following metal weight percentages of the catalyst:lithium from 0 to 5 weight % and aluminum from 0 to 15 weight %; In addition to their combinations with metal cations in concentrations of 0 to 40 weight % of the catalyst, such as magnesium, titanium, zinc, zirconium, gallium and silicon;organic or inorganic porosity promoters in concentrations of 0.05 to 25 weight % on wet base catalyst, such as polysaccharides;binders in concentrations of 1 to 20 weight % of the catalyst, such as clays, kaolin and metal oxides of the type MxOy,
where M = Al, Mg, Sr, Zr or Ti, among other metals of groups IA, IIA and IVB, X = 1 or 2 and y = 2 or 3, for the formation of particles of shape and size, such as extrudates, spheres, trilobules and raschig rings, among others;the catalyst have the following properties: surface area of 10 to 180 m2/g, pore volume of 0.1 to 0.5 cm3/g, and average pore diameter 100 to 200 Å. - Heterogeneous acid catalysts accordingly to claim 1, where the mixed metal salts in addition to their combinations with metal cations are preferably:a) Phosphates and Sulphates of lithium and aluminum;b) Phosphates and Sulphates of lithium, aluminum and titanium; yc) Phosphates and Sulphates of lithium, aluminum and magnesium.
- Heterogeneous acid catalysts accordingly to claims 1 and 2, wherein the heterogeneous acid catalysts are preferably composed of mixed metal salts with the following metal percentages weight of the catalyst: lithium from 0.1 to 3 weight % and aluminum from 0.3 to 10 weight %; in addition to their combinations with metallic cations, preferably titanium, magnesium and silicon, in concentrations of 0.2 to 30 weight %; porosity promoters preferably in concentrations of 0 to 12 weight % of the wet base catalyst; and binders, preferably clays in concentrations of 3 to 15 weight % of the catalyst.
- Heterogeneous acid catalysts accordingly to claims 1 to 3, wherein the polysaccharide used as the porosity promoter is preferably amylose-amylopectin (starch).
- Heterogeneous acid catalysts accordingly to claims 1 to 4, wherein the clays used as binders are preferably those of the montmorillonite type.
- Heterogeneous acid catalysts accordingly to claims 1 to 5, wherein the heterogeneous acid catalysts preferably have the following properties: surface area of 30 to 80 m2/g, pore volume of 0.1 to 0.3 cm3/g, and average pore diameter of 110 to 170 Å.
- The process for obtaining the heterogeneous acid catalysts of claims 1 to 6, comprises the following steps:a) The preparation of a hydrogel from the hydrolysis of aluminum lithium hydride, by the addition of water and an oxygenated solvent, such as an ether in an inert atmosphere, at temperature of -20 to 60° C and stirring from 0 to 10,000 rpm, generating a dispersion of lithium aluminum hydroxides in water and oxygenated solvent, with a pH of 10 to 16;b) the hydrogel or dispersion of lithium aluminum hydroxides in water and oxygenated solvent obtained in step a) is reacted with the corresponding acid to obtain the mixed metal salt, preferably lithium aluminum phosphate or sulfate. The acid is used in the necessary quantity to obtain the concentration of phosphorus or sulfur established;c) the suspension obtained in step b) is homogenized by stirring until having a crystalline solution;d) to the crystalline solution obtained in step c) is added the acetate solution corresponding to the metal cation to be integrated into the mixed metal salt of lithium and aluminum, such as magnesium, titanium, zinc, zirconium or gallium acetate; stirring for 2 to 8 hours, preferably for 2 to 3 hours, is maintained to homogenize;e) an organic or inorganic porosity promoter, such as a polysaccharide, is added to the homogenized solution obtained in step d), while agitation is maintained until homogenized;f) a binder is added to the homogenized solution obtained in step e), such as clay, kaolin or metal oxide of the MxOy type, where:M=Al, Mg, Sr, Zr or Ti, among other metals of the groups IA, IIA and IVB, x=1 or 2 and y=2 or 3, maintaining agitation until homogenization and subsequent aging and drying of the paste; yg) the paste obtained in step f) is extruded; the extrudates are dried at room temperature for 16 to 20 hours; then, the extrudates are fragmented to the desired size, preferably 3 to 4 cm in length; dried at 100-140° C for 2 to 4 hours and calcined at 250-500° C for 2 to 4 hours; finally, they are crushed and sifted.
- The process for obtaining the heterogeneous acid catalysts accordingly to claim 7, wherein the water used in step a) is preferably deionized water.
- The process for obtaining the heterogeneous acid catalysts accordingly to claims 7 and 8, wherein the oxygenated solvent used in step a) is preferably an ether, such as tetrahydrofuran, diethyl ether or dimethoxyethane.
- The process for obtaining the heterogeneous acid catalysts accordingly to claims 7 to 9, wherein the ether used as the oxygenated solvent in step a) is preferably anhydrous tetrahydrofuran (THF).
- The process for obtaining the heterogeneous acid catalysts accordingly to claims 7 to 10, wherein the addition of water and oxygenated solvent in step a) is carried out as a pre-prepared mixture in a volume ratio of 5:1 to 1:5, preferably at a rate of 1 drop per second.
- The process for obtaining the heterogeneous acid catalysts accordingly to claims 7 to 11, wherein the volume ratio of water to the aluminum lithium hydride used in step a) is from 3 to 20 parts of water per mole of aluminum Lithium hydride.
- The process for obtaining the heterogeneous acid catalysts accordingly to claims 7 to 12, wherein the inert atmosphere in step a) is preferably generated using gaseous nitrogen (N2), argon or helium.
- The process for obtaining the heterogeneous acid catalysts accordingly to claims 7 to 13, wherein the temperature used in step a) is preferably 0 to 5° C.
- The process for obtaining the heterogeneous acid catalysts accordingly to claims 7 to 14, wherein the corresponding acid employed in step b) is preferably added at a rate of 1 drop per second.
- The process for obtaining the heterogeneous acid catalysts accordingly to claims 7 to 15, wherein the acetate solution to be added in step d), corresponding to the metal cation to be integrated into the mixed metal salt of lithium and aluminum, is prepared just prior used as follow:reacting the alcohol, such as isopropoxide or ethoxide, with glacial acetic acid while stirring for 2 to 6 hours.
- The process for obtaining the heterogeneous acid catalysts accordingly to claims 7 to 16, wherein the acetates preferably employed in step d) are magnesium acetate and titanium acetate.
- The process for obtaining the heterogeneous acid catalysts accordingly to claims 7 to 17, wherein the agitation used in step d) to homogenize preferably is maintained for 2 to 3 hours.
- The process for obtaining the heterogeneous acid catalysts accordingly to claims 7 to 18, wherein the polysaccharide used as the porosity promoter in step e) is preferably amylose-amylopectin (starch).
- The process for obtaining the heterogeneous acid catalysts accordingly to claims 7 to 19, wherein the clay used as a binder in step f) is preferably of the montmorillonite, kaolin, silica or alumina type.
- The process for obtaining the heterogeneous acid catalysts accordingly to claims 7 to 20, wherein the mixed metal salts in addition to their combinations with preferably obtained metal cations are:
- The process for obtaining the heterogeneous acid catalysts accordingly to claims 7 to 21, wherein the process for the preparation of lithium and aluminum phosphates and sulphates does not comprise step d).
- Use of the heterogeneous acid catalysts of claims 1 to 22 in batch and continuous flow systems as promoters of reactions requiring moderate Lewis acidity in various industries, such as petroleum refining, petrochemical and chemical general.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX2016004132A MX2016004132A (en) | 2016-03-31 | 2016-03-31 | Process for obtaining heterogeneous acid catalysts based on mixed metal salts and use thereof. |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3225305A1 true EP3225305A1 (en) | 2017-10-04 |
EP3225305B1 EP3225305B1 (en) | 2024-05-22 |
Family
ID=58606009
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP17164236.6A Active EP3225305B1 (en) | 2016-03-31 | 2017-03-31 | Process for obtaining heterogeneous acid catalysts based on mixed metal salts and use thereof |
Country Status (4)
Country | Link |
---|---|
US (1) | US9999874B2 (en) |
EP (1) | EP3225305B1 (en) |
BR (1) | BR102017006532B1 (en) |
MX (1) | MX2016004132A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113845143B (en) * | 2021-09-23 | 2023-07-28 | 内江师范学院 | Bentonite modified metatitanic acid type lithium ion sieve precursor and preparation method thereof |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0103034A1 (en) * | 1982-09-09 | 1984-03-21 | The Dow Chemical Company | Crystalline lithium aluminates and a process for the preparation thereof |
US4789535A (en) * | 1984-04-13 | 1988-12-06 | Union Carbide Corporation | Lithium-aluminum-phosphorus-oxide molecular sieve compositions |
US5700946A (en) * | 1995-04-18 | 1997-12-23 | Nippon Shokubai Co., Ltd. | Process for production of N-vinyl compound |
US5908946A (en) | 1996-08-08 | 1999-06-01 | Institut Francais Du Petrole | Process for the production of esters from vegetable oils or animal oils alcohols |
CN103484258A (en) | 2013-09-22 | 2014-01-01 | 江苏大学 | Method for preparing biodiesel by using nano hydroxyapatite to catalyze triglyceride |
CN103706384A (en) | 2013-12-24 | 2014-04-09 | 内蒙古农业大学 | Preparation method of bio-diesel catalyst |
CN103752297A (en) | 2014-01-03 | 2014-04-30 | 南昌大学 | Zirconium-oxide catalyst for producing biodiesel, as well as preparation method and application of zirconium-oxide catalyst |
CN103801282A (en) | 2012-11-12 | 2014-05-21 | 中国科学院大连化学物理研究所 | Solid base catalyst as well as preparation and application thereof |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102009049693A1 (en) * | 2009-10-16 | 2011-04-21 | Süd-Chemie AG | Pure phase lithium aluminum titanium phosphate and process for its preparation and use |
WO2013177461A2 (en) * | 2012-05-24 | 2013-11-28 | Siluria Technologies, Inc. | Catalytic forms and formulations |
-
2016
- 2016-03-31 MX MX2016004132A patent/MX2016004132A/en unknown
-
2017
- 2017-03-29 BR BR102017006532-4A patent/BR102017006532B1/en active IP Right Grant
- 2017-03-30 US US15/474,795 patent/US9999874B2/en active Active
- 2017-03-31 EP EP17164236.6A patent/EP3225305B1/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0103034A1 (en) * | 1982-09-09 | 1984-03-21 | The Dow Chemical Company | Crystalline lithium aluminates and a process for the preparation thereof |
US4789535A (en) * | 1984-04-13 | 1988-12-06 | Union Carbide Corporation | Lithium-aluminum-phosphorus-oxide molecular sieve compositions |
US5700946A (en) * | 1995-04-18 | 1997-12-23 | Nippon Shokubai Co., Ltd. | Process for production of N-vinyl compound |
US5908946A (en) | 1996-08-08 | 1999-06-01 | Institut Francais Du Petrole | Process for the production of esters from vegetable oils or animal oils alcohols |
CN103801282A (en) | 2012-11-12 | 2014-05-21 | 中国科学院大连化学物理研究所 | Solid base catalyst as well as preparation and application thereof |
CN103484258A (en) | 2013-09-22 | 2014-01-01 | 江苏大学 | Method for preparing biodiesel by using nano hydroxyapatite to catalyze triglyceride |
CN103706384A (en) | 2013-12-24 | 2014-04-09 | 内蒙古农业大学 | Preparation method of bio-diesel catalyst |
CN103752297A (en) | 2014-01-03 | 2014-04-30 | 南昌大学 | Zirconium-oxide catalyst for producing biodiesel, as well as preparation method and application of zirconium-oxide catalyst |
Non-Patent Citations (14)
Title |
---|
BB BAKER; WM MACNEVIN: "Lithium Aluminum Hydride as Reagent for Determination of Water", ANAL. CHEM., vol. 22, 1950, pages 364 - 365 |
CAETANO ET AL.: "Esterification of free fatty acids with methanol using heteropolyacids immobilized on silica", CATAL COMMUN, vol. 9, 2008, pages 1996 - 1999, XP022683655, DOI: doi:10.1016/j.catcom.2008.03.036 |
DE FILIPPIS ET AL., ENERGY & FUELS, vol. 19, no. 6, 2005, pages 2225 - 2228 |
HORAN HA; DAMIANO JB: "The Formation and Composition of Lithium Aluminate", J. AM. CHEM. SOC., vol. 57, 1935, pages 2434 - 2436 |
JUAN A. MELERO ET AL.: "Critical Review, Heterogeneous acid catalysts for biodiesel production: current status and future challenges", GREEN CHEM., vol. 11, 2009, pages 1285 - 1308 |
KATADA N. ET AL., APPLIED CATALYSIS A GENERAL, vol. 363, 2009, pages 164 - 168 |
OBADIAH ET AL., BIORESOURCE TECHNOLOGY, vol. 116, 2012, pages 512 - 516 |
OLIVEIRA CF ET AL.: "Esterification of oleic acid with ethanol by 12-tungstophosphoric acid supported on zirconia", APPL CATAL A-GEN, vol. 372, 2010, pages 153 - 161, XP026798936 |
RATTANAPHRA ET AL.: "Simultaneous Conversion of Triglyceride / Free Fatty Acid Mixtures into Biodiesel Using Sulfated Zirconia", TOP CATAL, vol. 53, 2010, pages 773 - 782, XP019831504 |
SHI ET AL., CHEMICAL ENGINEERING & TECHNOLOGY, vol. 35, no. 2, 2012, pages 347 - 352 |
XIAN MING WU ET AL: "Synthesis of Li1.3Al0.3Ti1.7(PO4)3 by sol-gel technique", MATERIALS LETTERS, ELSEVIER, AMSTERDAM, NL, vol. 58, no. 7-8, March 2004 (2004-03-01), pages 1227 - 1230, XP002617467, ISSN: 0167-577X, [retrieved on 20031027], DOI: 10.1016/J.MATLET.2003.09.013 * |
XIE ET AL., BIORESOURCE TECHNOLOGY, vol. 119, 2012, pages 60 - 65 |
YAN: "Advances in Heterogeneous Catalysis for Biodiesel Synthesis", TOP CATAL., vol. 53, 2010, pages 721 - 736 |
YIN ET AL., FUEL, vol. 93, 2012, pages 284 - 287 |
Also Published As
Publication number | Publication date |
---|---|
BR102017006532A2 (en) | 2020-04-28 |
EP3225305B1 (en) | 2024-05-22 |
BR102017006532B1 (en) | 2022-03-15 |
US20170282163A1 (en) | 2017-10-05 |
MX2016004132A (en) | 2017-09-29 |
US9999874B2 (en) | 2018-06-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Mansir et al. | Investigation of heterogeneous solid acid catalyst performance on low grade feedstocks for biodiesel production: A review | |
Zhou et al. | Nano La2O3 as a heterogeneous catalyst for biodiesel synthesis by transesterification of Jatropha curcas L. oil | |
Taufiq-Yap et al. | Biodiesel production via transesterification of palm oil using NaOH/Al2O3 catalysts | |
Sharma et al. | Latest developments on application of heterogenous basic catalysts for an efficient and eco friendly synthesis of biodiesel: A review | |
Tantirungrotechai et al. | Biodiesel synthesis over Sr/MgO solid base catalyst | |
Sahani et al. | Studies on fast and green biodiesel production from an indigenous nonedible Indian feedstock using single phase strontium titanate catalyst | |
Vahid et al. | Effect of alumina loading on the properties and activity of SO42−/ZrO2 for biodiesel production: process optimization via response surface methodology | |
Xie et al. | Transesterification of soybean oil over WO3 supported on AlPO4 as a solid acid catalyst | |
Yadav et al. | Transesterification of used vegetable oil using BaAl2O4 spinel as heterogeneous base catalyst | |
Wang et al. | Ordered mesoporous carbon supported ferric sulfate: a novel catalyst for the esterification of free fatty acids in waste cooking oil | |
Kesica et al. | Mechanochemically synthesized CaO ZnO catalyst for biodiesel production | |
Popova et al. | Glycerol acetylation on mesoporous KIL-2 supported sulphated zirconia catalysts | |
US20100139152A1 (en) | Heterogeneous catalysts for mono-alkyl ester production, method of making, and method of using same | |
Pradhan et al. | Optimal efficient biodiesel synthesis from used oil employing low-cost ram bone supported Cr catalyst: Engine performance and exhaust assessment | |
Ong et al. | Synthesis and characterization of a CaFe 2 O 4 catalyst for oleic acid esterification | |
Amirthavalli et al. | Production of biodiesel from waste cooking oil using MgO nanocatalyst | |
Reinoso et al. | Synthesis of biodiesel from soybean oil using zinc layered hydroxide salts as heterogeneous catalysts | |
Lu et al. | Solvent-free oxidative cleavage of epoxy fatty acid methyl esters by a “release and capture” catalytic system | |
EP3225305B1 (en) | Process for obtaining heterogeneous acid catalysts based on mixed metal salts and use thereof | |
Pampararo et al. | Sodium aluminate-catalyzed biodiesel synthesis | |
Zhu et al. | Preparation and characterization of a novel bifunctional heterogeneous Sr–La/wollastonite catalyst for biodiesel production | |
Lu et al. | Transesterification of vegetable oil to biodiesel over Mgo-Li2O catalysts templated by a PDMS-PEO comb-like copolymer | |
Azmoon et al. | Fabrication of nanosized SO 4 2−/Co–Al mixed oxide via solution combustion method used in esterification reaction: effect of urea-nitrate ratio on the properties and performance | |
BRPI1003931A2 (en) | heterogeneous zinc superstoichiometric zinc spinumin aluminate catalyst and its use in a preparation process for the preparation of alcoholic esters from triglycerides and alcohols | |
Nayebzadeh et al. | Influence of fuel to oxidizer ratio on microwave-assisted combustion preparation of nanostructured KOH/Ca12Al14O33 catalyst used in efficient biodiesel production |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: ROSAS, CELIA MARIN Inventor name: CRUZ, FEDERICO JESUS JIMENEZ Inventor name: GUEVARA, FLORENTINO RAFAEL MURRIETA Inventor name: LOPEZ, LUIS CARLOS CASTANEDA Inventor name: GUERRERO, MARIA DEL CARMEN MARTINEZ Inventor name: SUAREZ, ROGELIO HERNANDEZ Inventor name: RODRIGUEZ, JAVIER ESTEBAN RODRIGUEZ Inventor name: JACOB, ALICIA DEL RAYO JARAMILLO |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20171212 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20200709 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230531 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: B01J 35/04 20060101ALN20231110BHEP Ipc: B01J 37/08 20060101ALN20231110BHEP Ipc: B01J 37/04 20060101ALN20231110BHEP Ipc: B01J 37/03 20060101ALN20231110BHEP Ipc: C01F 7/043 20220101ALI20231110BHEP Ipc: C10G 3/00 20060101ALI20231110BHEP Ipc: C11C 3/10 20060101ALI20231110BHEP Ipc: C01F 7/76 20060101ALI20231110BHEP Ipc: C01B 25/45 20060101ALI20231110BHEP Ipc: B01J 37/00 20060101ALI20231110BHEP Ipc: B01J 35/10 20060101ALI20231110BHEP Ipc: B01J 27/055 20060101ALI20231110BHEP Ipc: B01J 23/00 20060101ALI20231110BHEP Ipc: B01J 27/18 20060101AFI20231110BHEP |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20240105 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602017082053 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |